Facile Synthesis of Gram-Scale Mesoporous Ag/TiO₂ Photocatalysts for Pharmaceutical Water Pollutant Removal and Green Hydrogen Generation

Abstract

This work demonstrates a two-step gram-scale synthesis of presynthesized silver (Ag) nanoparticles impregnated with mesoporous TiO₂ and evaluates their feasibility for wastewater treatment and hydrogen gas generation under natural sunlight. Paracetamol was chosen as the model pharmaceutical pollutant for evaluating photocatalytic performance. A systematic material analysis (morphology, chemical environment, optical bandgap energy) of the Ag/TiO₂ photocatalyst powder was carried out, and the influence of material properties on the performance is discussed in detail. The experimental results showed that the decoration of anatase TiO₂ nanoparticles (size between 80 and 100 nm) with 5 nm Ag nanoparticles (1 wt %) induced visible-light absorption and enhanced charge carrier separation. As a result, 0.01 g/L Ag/TiO₂ effectively removed 99% of 0.01 g/L paracetamol in 120 min and exhibited 60% higher photocatalytic removal than pristine TiO₂. Alongside paracetamol degradation, Ag/TiO₂ led to the generation of 1729 μmol H₂ g^-1 h^-1. This proof-of-concept approach for tandem pollutant degradation and hydrogen generation was further evaluated with rare earth metal (lanthanum)- and nonmetal (nitrogen)-doped TiO₂, which also showed a positive response. Using a combination of <i>ab initio</i> calculations and our new theory model, we revealed that the enhanced photocatalytic performance of Ag/TiO₂ was due to the surface Fermi-level change of TiO₂ and lowered surface reaction energy barrier for water pollutant oxidation. This work opens new opportunities for exploiting tandem photocatalytic routes beyond water splitting and understanding the simultaneous reactions in metal-doped metal oxide photocatalyst systems under natural sunlight.